DE102015211829A1 - Use of new Naphthol AS pigment mixtures in printing materials - Google Patents

Abstract

worin unabhängig voneinander
X¹, X³ Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl oder Di(C₁-C₄)-Alkylsulfamoyl;
X², X⁴ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy Halogen oder Nitro;
Y¹, Y² Wasserstoff, Halogen oder C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₁-C₄-Alkoxycarbonyl; und
Z¹, Z² Wasserstoff, Phenyl, Naphthyl, Benzimidazolonyl, substituiertes Phenyl oder substituiertes Naphthyl, wobei die Substituenten 1, 2, 3 oder 4 an der Zahl und ausgewählt aus der Gruppe Halogen, Nitro, Cyano, C₁-C₄-Alkoxycarbonyl, Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Phenylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl, Di(C₁-C₄)-Alkylsulfamoyl, C₁-C₄-Acylamino, C₁-C₄-Alkyl und C₁-C₄-Alkoxy sind, bedeuten, und wobei die Pigmente der Formeln (Ia) und (Ib) verschieden sind.
als Farbmittel in Druckverfahren.The invention relates to the use of pigment mixtures which in each case contain at least one pigment of the formulas (Ia) and (Ib),

wherein independently of one another
X ¹ , X ³ carbamoyl, C ₁ -C ₄ alkylcarbamoyl, di (C ₁ -C ₄ ) alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ alkylsulfamoyl or di (C ₁ -C ₄ ) alkylsulfamoyl;
X ² , X ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro;
Y ¹ , Y ^{2 are} hydrogen, halogen or C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl; and
Z ¹ , Z ^{2 is} hydrogen, phenyl, naphthyl, benzimidazolonyl, substituted phenyl or substituted naphthyl, wherein the substituents 1, 2, 3 or 4 in the number and selected from the group halogen, nitro, cyano, C ₁ -C ₄ alkoxycarbonyl , Carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl, di (C ₁ -C ₄ ) -alkylsulfamoyl, C ₁ - C ₄ acylamino, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and wherein the pigments of the formulas (Ia) and (Ib) are different.
as a colorant in printing processes.

Description

The present invention relates to the use of novel naphthol AS pigment mixtures in printing processes, in particular for electrophotographic toners, ink-jet printing, in the production of color filters and in conventional printing inks.

In electrophotographic recording processes, a "latent charge image" is formed on a photoconductor. This "latent charge image" is developed by applying an electrostatically charged toner, which is then transferred, for example, to paper, textiles, films or plastic and fixed for example by means of pressure, radiation, heat or solvent action. Typical toners are one- or two-component powder toners (also called one- or two-component developers), in addition, special toners such. As magnetic or liquid toner and polymerization toner, in use.

As coloring component in color toners typically organic color pigments are used. Color pigments have significant advantages over dyes because of their insolubility in the application medium, such. B. better thermal stability and light fastness.

In the so-called conventional toner production processes, the colorants are incorporated (dispersed) by means of extruding or kneading into the toner binders together with other toner ingredients, such as charge control agents and waxes. For the production of toners, it is important in practice that the colorants have sufficient thermal stability and good dispersibility in the respective toner binder. Typical incorporation temperatures for colorants in the toner resins are between 70 and 200 ° C when using kneaders or extruders. Accordingly, a thermal stability of 200 ° C, better 250 ° C, of great advantage. It is also important that the thermal stability over a longer period (about 30 minutes) and in various binder systems is guaranteed. Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene acrylate, styrene butadiene, acrylate, polyester, phenolic epoxy resins, polysulfones, polyurethanes, individually or in combination, which contain other ingredients, such as charge control agents, waxes or Flow aid, may contain or may be added afterwards.

In addition to the described process of toner production in a physical mixing process, modern toners are made using various so-called chemical processes in which the toner polymer is prepared in a polymerization reaction from suitable monomers or oligomers in the presence of the other ingredients (colorant, charge control agent, wax, etc.) and by incorporating said ingredients. Furthermore, there are processes in which the desired toner particles are obtained by aggregating polymer particles in the nanometer range into larger particles in the micrometer range, including the mentioned toner ingredients.

These processes have in common that the toner ingredients and thus the colorant must be incorporated in a liquid medium and finely distributed (dispersed) must be present. As a rule, a multiphase system (water / monomers, oligomers or water / solvent / monomer or oligomer or a latex) is present.

The compatibility and good dispersibility of the ingredients used with the reaction media used in said chemical toner production processes is of great importance for the quality of the toner. So it affects z. As the chargeability, transparency and color purity, but also the effectiveness of the manufacturing process (the ingredients must not interfere, for example, the polymerization reaction).

Liquid toners usually consist of a nonpolar solvent, in which the actual toner particles are finely distributed in the micrometer range. Here, special demands are placed on the solvent resistance of the ingredients. Likewise, the comments made above on the compatibility and dispersibility in the carrier used apply.

The ink-jet or ink-jet process is a contactless printing process in which droplets of the recording liquid are directed from one or more nozzles onto the substrate to be printed. In order to obtain prints of excellent quality, the recording liquids and the colorants contained therein must meet high requirements, in particular also with regard to the desired color shade and the reliability during the printing process. In addition to dye-based inks, intensively pigmented inks are also used in ink-jet printing. The fineness of the pigments contained in the inks is a prerequisite for their application in ink-jet printing, on the one hand to prevent clogging of the nozzles, but also to achieve a high transparency and a desired color.

Ink jet inks can be prepared by adding a pigment composition into the aqueous or nonaqueous medium, into the microemulsion medium, or into the medium for making the UV curable ink, or into the wax to make a hot melt ink jet Ink is dispersed. Advantageously, the printing inks thus obtained are subsequently filtered for ink-jet applications (for example via a 1 μm filter).

Common to all printing applications is the principle of subtractive color mixing, where all the color spectrum visible to the human eye is created by mixing the primary colors yellow, cyan, and magenta. Only if the respective primary color meets the well-defined color requirements, an exact color reproduction is possible. Otherwise, some hues may not be reproduced and the color contrast is insufficient. For the subtractive color mixing, it is also important that the individual primary shades have the highest possible color purity in order to achieve a brilliant color rendering.

Basically, there is a need for a magenta pigment which has the highest possible transparency, blue tintability, high color purity and good dispersibility in printing materials, in particular in toner polymers or chemical toner production media, in ink jet ink systems and printing ink media, but also in electronic inks. or "e-inks") or "electronic paper" ("e-paper").

Transparency is central because in full color printing (in both classic and digital printing processes, such as electrophotography and inkjet printing), the colors yellow, cyan, and magenta are printed on top of each other, with the order of the colors being different Machine depends. If an above-lying color is not transparent enough, the underlying color can not show through sufficiently and the color rendering is distorted.

For the representation of the magenta hue, various magenta pigments are currently being used in the toners, inkjet inks and printing inks used. Pigments from the quinachridone series (PR 122, PV 19) are widely used, especially in inkjet printing and in electrophotography , Chinachridon pigments are well suited for this application due to their bluish magenta tint at very high chroma levels. However, they are relatively weak in color, whereby the amount used in the ink or the toner must be increased in order to achieve a sufficient color depth. On the other hand, with increased pigment concentration in the printing inks and toners, the rheological and other application-relevant properties are adversely affected. As an alternative to quinacridones, azo pigments are used in inks and toners as well as printing inks. Known azo pigments such. B. P. R. 146, 147, 185, 269 are significantly stronger in color than quinacridones, but can not cover the very bluish magenta area of the color space and are also less pure in color. Often, combinations of quinacridone and azo pigments are used to obtain the desired hue.

It is an object of the present invention to provide a very inexpensive, transparent, bluish and brilliant azo colorant with good dispersibility and high thermal stability for use in electrophotographic toners and developers, inkjet inks, color filters and printing inks.

It has surprisingly been found that the combinations of various naphthol AS pigments described below achieve the object according to the invention.

worin unabhängig voneinander
X¹, X³ Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl oder Di(C₁-C₄)-Alkylsulfamoyl;
X², X⁴ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy Halogen oder Nitro;
Y¹, Y² Wasserstoff, Halogen oder C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₁-C₄-Alkoxycarbonyl; und
Z¹, Z² Wasserstoff, Phenyl, Naphthyl, Benzimidazolonyl, substituiertes Phenyl oder substituiertes Naphthyl, wobei die Substituenten 1, 2, 3 oder 4 an der Zahl und ausgewählt aus der Gruppe Halogen, Nitro, Cyano, C₁-C₄-Alkoxycarbonyl, Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Phenylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl, Di(C₁-C₄)-Alkylsulfamoyl, C₁-C₄-Acylamino, C₁-C₄-Alkyl und C₁-C₄-Alkoxy sind, bedeuten, und wobei die Pigmente der Formeln (Ia) und (Ib) verschieden sind.
als Farbmittel in Druckverfahren.The present invention relates to the use of mixtures of naphthol AS pigments which each contain at least one naphthol AS pigment of the formulas (Ia) and (Ib),

wherein independently of one another
X ¹ , X ³ carbamoyl, C ₁ -C ₄ alkylcarbamoyl, di (C ₁ -C ₄ ) alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ alkylsulfamoyl or di (C ₁ -C ₄ ) alkylsulfamoyl;
X ² , X ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro;
Y ¹ , Y ^{2 are} hydrogen, halogen or C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl; and
Z ¹ , Z ^{2 is} hydrogen, phenyl, naphthyl, benzimidazolonyl, substituted phenyl or substituted naphthyl, wherein the substituents 1, 2, 3 or 4 in the number and selected from the group halogen, nitro, cyano, C ₁ -C ₄ alkoxycarbonyl , Carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl, di (C ₁ -C ₄ ) -alkylsulfamoyl, C ₁ - C ₄ acylamino, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and wherein the pigments of the formulas (Ia) and (Ib) are different.
as a colorant in printing processes.

In the above formulas
X ¹ , X ^{3 are} preferably carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, more preferably carbamoyl, C ₁ -C ₂ -alkylcarbamoyl or di (C ₁ -C ₂ ) -alkylcarbamoyl.

In the above formulas
X ² , X ^{4 are} preferably hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, particularly preferably hydrogen.

In the above formulas
Y ¹ , Y ^{2 are} preferably C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, particularly preferably methyl, ethyl, methoxy or ethoxy.

In the above formulas
Z ¹ , Z ^{2 is} preferably hydrogen, phenyl, or phenyl substituted with nitro, cyano, halogen, C ₁ -C ₄ -alkyl and / or C ₁ -C ₄ -alkoxy, more preferably phenyl or with nitro, methyl, ethyl, methoxy and / or ethoxy-substituted phenyl.

worin unabhängig voneinander
X¹ Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl oder Di(C₁-C₄)-Alkylsulfamoyl;
X² Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Nitro;
Y Wasserstoff, Halogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₁-C₄-Alkoxycarbonyl; und
Z¹, Z² Wasserstoff, Phenyl, Naphthyl, Benzimidazolonyl, substituiertes Phenyl oder substituiertes Naphthyl, wobei die Substituenten 1, 2, 3 oder 4 an der Zahl und ausgewählt aus der Gruppe Halogen, Nitro, Cyano, C₁-C₄-Alkoxycarbonyl, Carbamoyl, C₁-C₄-Alkylcarbamoyl, Di(C₁-C₄)-Alkylcarbamoyl, Phenylcarbamoyl, Sulfamoyl, Phenylsulfamoyl, C₁-C₄-Alkylsulfamoyl, Di(C₁-C₄)-Alkylsulfamoyl, C₁-C₄-Acylamino, C₁-C₄-Alkyl und C₁-C₄-Alkoxy sind, bedeuten, und wobei die Pigmente der Formeln (IIa) und (IIb) verschieden sind.Preferred for the purposes of the present invention are mixtures of naphthol AS pigments, which in each case contain at least one naphthol AS pigment of the formulas (IIa) and (IIb),

wherein independently of one another
X ^{1 is} carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl or di (C ₁ -C ₄ ) -alkylsulfamoyl;
X ^{2 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro;
Y is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl; and
Z ¹ , Z ^{2 is} hydrogen, phenyl, naphthyl, benzimidazolonyl, substituted phenyl or substituted naphthyl, wherein the substituents 1, 2, 3 or 4 in the number and selected from the group halogen, nitro, cyano, C ₁ -C ₄ alkoxycarbonyl , Carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl, di (C ₁ -C ₄ ) -alkylsulfamoyl, C ₁ - C ₄ acylamino, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and wherein the pigments of the formulas (IIa) and (IIb) are different.

Particularly preferred are mixtures described above, wherein X ^{2 has} the meaning of hydrogen.

Very particularly preferred are mixtures described above, wherein X ^{2 has} the meaning of hydrogen and X ^{1 is} in the para position to Y.

In the above formulas, halogen is preferably F, Cl or Br, especially Cl.

worin unabhängig voneinander
X¹ die Bedeutung Carbamoyl, C₁-C₂-Alkylcarbamoyl oder Di(C₁-C₂)-Alkylcarbamoyl;
Y die Bedeutung Methyl, Methoxy, Ethyl oder Ethoxy;
Z¹ die Bedeutung Phenyl oder mit ein, zwei oder drei Resten aus der Gruppe Methyl, Ethyl, Methoxy, Ethoxy, Chlor substituiertes Phenyl;
Z² die Bedeutung Nitrophenyl oder Cyanophenyl haben.Particularly preferred for the purposes of the invention are mixtures of naphthol AS pigments, each containing at least one naphthol AS pigment of the formulas (IIIa) and (IIIb),

wherein independently of one another
X ^{1 is} carbamoyl, C ₁ -C ₂ -alkylcarbamoyl or di (C ₁ -C ₂ ) -alkylcarbamoyl;
Y is methyl, methoxy, ethyl or ethoxy;
Z ^{1 is} phenyl or phenyl substituted by one, two or three radicals selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine;
Z ^{2 have} the meaning nitrophenyl or cyanophenyl.

Of particular interest are mixtures of naphthol AS pigments, each containing at least one naphthol AS pigment of the above formulas (IIIa) and (IIIb), wherein
X ^{1 is} carbamoyl, methylcarbamoyl or ethylcarbamoyl;
Y is methoxy or ethoxy;
Z ^{1 is} methylphenyl, ethylphenyl, methoxyphenyl or ethoxyphenyl; and
Z ^{2 have} the meaning nitrophenyl or cyanophenyl.

Of particular interest are mixtures of naphthol AS pigments, each containing at least one naphthol AS pigment of the above formulas (IIIa) and (IIIb) wherein
X ^{1 is} carbamoyl or methylcarbamoyl;
Y is methoxy;
Z ^{1 is} methylphenyl, in particular o-methylphenyl; and
Z ^{2 has} the meaning nitrophenyl, in particular m-nitrophenyl.

The pigment mixtures used according to the invention expediently contain 1 to 99% by weight of one Component of the formula (Ia), (IIa) or (IIIa) and 99 to 1 wt .-% of a component of formula (Ib), (IIb) or (IIIb), preferably 5 to 95 wt .-% of a component of the formula (Ia), (IIb) or (IIIa) and 95 to 5 wt .-% of a component of formula (Ib), (IIb) or (IIIb), particularly preferably 10 to 90 wt .-% of a component of formula (Ia ), (IIa) or (IIIa) and 90 to 10% by weight of a component of the formula (Ib), (IIb) or (IIIb), very particularly preferably 25 to 75% by weight of a component of the formula (Ia) , (IIa) or (IIIa) and 75 to 25 wt .-% of a component of formula (Ib), (IIb) or (IIIb), in particular 40 to 60 wt .-% of a component of formula (Ia), (IIa ) or (IIIa) and 60 to 40 wt .-% of a component of formula (Ib), (IIb) or (IIIb), each based on the total weight of the pigment mixture.

worin
X¹, X², Y eine der oben angegebenen Bedeutungen besitzt und
M für Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder für Ammonium steht.The pigment mixtures used according to the invention optionally contain one or more additional colorants of the general formula (IV) in proportions of up to 10% by weight, for example from 0.1 to 10% by weight, based on the total weight of the pigment mixture,

wherein
X ¹ , X ² , Y has one of the meanings given above and
M is hydrogen, an alkali metal, an alkaline earth metal or ammonium.

worin Z¹ und Z² eine der oben angegebenen Bedeutungen besitzen.In addition, the pigment mixtures used according to the invention may optionally contain one or more residual couplers from the group of the β-naphthol derivatives of the general formulas (VIa) and / or (VIb) in proportions of up to 10% by weight, for example of 0.1 to 10% by weight, based on the total weight of the pigment mixture, of

wherein Z ¹ and Z ^{2 have} one of the meanings given above.

in saurem Medium und anschließende Kupplung der so erhaltenen Diazoniumverbindungen auf eine Mischung aus mindestens zwei Kupplungskomponenten der Formeln (VIa) und (VIb)

The pigment mixtures used according to the invention can be prepared by diazotization of amines of the formulas (Va) and (Vb)

in an acidic medium and subsequent coupling of the diazonium compounds thus obtained to a mixture of at least two coupling components of the formulas (VIa) and (VIb)

Subsequently, the resulting pigment suspension can be filtered and the resulting moist presscake is expediently dried to constant weight.

In the case where the amines of the formulas (Va) and (Vb) are the same, two equivalents of the relevant amine are correspondingly diazotized and coupled as described above.

The diazotization and coupling can be carried out according to generally known methods and are described in German Patent Application No. filed on the same date (R 6380).

The pigment mixtures used in the present invention may also contain adjuvants such as surfactants, pigmentary and nonpigmentary dispersants, fillers, modifiers, resins, waxes, defoamers, anti-dusting agents, extenders, colorants for colorants, preservatives, drying retardants, rheology control additives, wetting agents, antioxidants, UV Absorbers, light stabilizers or a combination thereof.

The addition of the adjuvant can be carried out at any time before, during or after the reaction / synthesis, all at once or in several portions. The aids can be added, for example, directly to the solutions or suspensions of the reactants, but also during the reaction in liquid, dissolved or suspended form.

The total amount of auxiliaries added may be from 0 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight, based on the total weight of the pigment mixture plus auxiliary.

Suitable surfactants are anionic or anionic, cationic or cationic and nonionic substances or mixtures of these agents.

Examples of surfactants, pigmentary and non-pigmentary dispersants which can be used in the process according to the invention are described in US Pat EP-A-1 195 411 specified.

Suitable colorants for shading z. As pigments from the group of azo and / or polycyclic pigments are selected, for. Yellow pigments such as C.I. Pigment Yellow 155, P.Y. 139, P.Y.83, P.Y.181, P.Y.191, P.Y.75, P.Y. 180 or P.Y.97; Orange pigments such as Pigment Orange 62, P.O. 36, P.O. 34, P.O. 13, P.O. 36, P.O. 13, P.O. 43, P.O. 5 or P.O. 73; red / magenta pigments such as Pigment Red 57, PR 48, PR 122, PR 146, PR 147, PR 269, PR 154, PR 185, PR 184, PR 192, PR 202, PR 207, PR 206, PR 209 or PR 254; and violet pigments such as Pigment Violet 19, P.V. 23, P.V. 29, P.V. 35 or P.V. 37, P.V. 42, P.V. 57 and also blue pigments such as Pigment Blue 15, P.B. 60 or P.B. 80.

Chinachridones z. B. are particularly preferred as mixing partners. B. P.R. 122, P.R. 202, P.V. 19 and quinacridone mixed crystals of two or more components, as well as other azo pigments from the group of naphthol-AS pigments, such as. P.R. 184, P.R. 185, P.R. 176, P.R. 269, P.R. 146, P.R. 147, P.R. 150.

Preferred dyes which can be used to shade the pigment mixtures according to the invention are water-soluble dyes from the group of direct, reactive and acid dyes, and also dyes from the series of solvent dyes (solvent dyes), disperse dyestuffs and vat dyes (Vat Dyes). Specific examples mentioned are CI Reactive Yellow 37, Acid Yellow 23, Reactive Red 23, 180, Acid Red 52, 92 Reactive Blue 19, 21, Acid Blue 9, Direct Blue 199, Solvent Yellow 14, 16, 25, 56, 64, 79, 81, 82, 83: 1, 93, 98, 133, 162, 174, Solvent Red 8, 19, 24, 49, 52, 89, 90, 91, 109, 118, 119, 122, 127, 135, 149, 160, 195, 196, 197, 212, 215, Solvent Blue 44, 45, Solvent Orange 60, 63, Disperse Yellow 64, Disperse Red 11, Vat Red 41, Vat Violet 3, Basic Red 1, Basic Violet 10.11.

In the following, the pigment composition used according to the invention refers to the naphthol AS pigment mixtures used according to the invention, which optionally contain one or more of the abovementioned auxiliaries.

When used in toners, inkjet inks, color filters, and ink systems, the pigment compositions of the present invention provide bluish magenta shades that are ideally suited for subtractive color mixing. In this case, the pigment compositions according to the invention can be used both as the sole colorant and in mixtures with other pigments or dyes, as described above.

For the purposes of the present invention, both classic printing processes on paper, cardboard, textiles or plastics, such as. B. offset printing, flexographic printing or gravure printing, as well as non-impact printing method, such. As in electrophotography, in ink-jet printing, electronic inks and the production of color filters understood.

The present invention is further an ink, z. Example, an offset printing, flexographic or gravure ink containing a pigment composition described above, advantageously in a concentration of 5 to 15 wt .-%, based on the total weight of the ink.

The present invention furthermore relates to an electrophotographic toner or developer comprising a pigment composition described above, expediently in a concentration of 1 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the toner or developer. Toners and developers are, for example, one- or two-component powder toners (also known as one- or two-component developers), magnetic toners, liquid toners, latextoners, polymerization toners and special toners. These can be used both in the so-called conventional toner production processes by means of extrusion but also in chemical toner production processes such as emulsion aggregation, suspension polymerization or others. In contrast to the classical toner production process in which the pigment is incorporated into a toner carrier material (polystyrene, polyester or the like) together with other ingredients, pigments in the chemical toner processes usually have to be in liquid media (eg by means of a bead mill). be finely dispersed.

The present invention further provides an inkjet ink containing a pigment composition as described above, preferably in a concentration of 0.5 to 50 wt .-%, preferably 1 to 30 wt .-%, based on the total weight of the inkjet ink. As ink-jet inks, there are those on aqueous and non-aqueous basis, microemulsion inks, UV inks and inks that work according to the hot-melt process

Water-based inkjet inks contain substantially 0.5 to 30 wt .-%, preferably 1 to 15 wt .-% of the pigment composition, 70 to 95 wt .-% of deionized water, suitable dispersants, optionally carrier polymer and / or humectants.

Solvent-based ink-jet inks contain essentially 0.5 to 30% by weight, preferably 1 to 15% by weight, of the pigment composition, 70 to 95% by weight of an organic solvent or solvent mixture and / or a hydrotrope compound , Optionally, the solvent-based ink-jet inks may contain carrier materials and binders which are soluble in the "solvent", such as e.g. As polyolefins, natural and synthetic rubber, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, polyvinyl butyrals, wax / latex systems or combinations of these compounds.

Optionally, the solvent-based ink-jet inks may contain other additives such. As wetting agents, degasser / defoamers, preservatives and antioxidants.

Microemulsion inks are based on organic solvents, water and optionally a surfactant. Microemulsion inks contain suitably 0.5 to 30 wt .-%, preferably 1 to 15 wt .-%, of the pigment composition, 0.5 to 95 wt .-% water and 0.5 to 95 wt .-% organic solvent and / or interface mediator.

UV inks typically consist of monomers of low molecular weight mono-, di-, tri-, tetra-, and / or penta-functional acrylates and / or acrylate, urethane, epoxy, or polyester-based oligomers. The UV inks are typically initiated cationically, anionically, or radically.

UV-curable inks contain substantially 0.5 to 30% by weight of the pigment composition, 0.5 to 95% by weight of water, 0.5 to 95% by weight of an organic solvent or solvent mixture, 0.5 to 50 Wt .-% of a radiation-curable binder and 0 to 10 wt .-% of a photoinitiator.

Hot-melt inks are usually based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and liquid when heated, with the preferred melting range between about 60 ° C and about 140 ° C. Hot-melt ink-jet inks consist essentially of 20 to 90 wt .-% wax and 1 to 10 wt .-% of the pigment composition. Furthermore, 0 to 20 wt .-% of an additional polymer (as a "dye remover"), 0 to 5 wt .-% dispersant, 0 to 20 wt .-% viscosity modifier, 0 to 20 wt .-% plasticizer, 0 to 10 wt % Of tackiness additive, 0 to 10% by weight of transparency stabilizer (prevents, for example, the crystallization of the wax) and 0 to 2% by weight of antioxidant.

The toners and developers according to the invention and inkjet inks are usually used in Tonerkartensensets or in ink sets consisting of yellow, magenta, cyan and black toners or inks containing as colorants correspondingly colored pigments and / or dyes. Furthermore, they can be used in toner or ink sets, which additionally contain one or more spot colors, for example orange, green, blue and / or special colors (gold, silver).

Preference is given to a set of printing inks or toner cartridges whose black preparation preferably contains carbon black as a colorant, in particular a gas or Furnaceruß; its cyan preparation containing one or more pigments from the group of phthalocyanine pigments, optionally nuanced with Pigment Blue 16, Pigment Blue 56, Pigment Blue 60 or Pigment Blue 61; whose magenta preparation preferably contains a pigment composition according to the invention, optionally nuanced with a pigment from the group of the monoazo, disazo, β-naphthol, naphthol AS, laked azo, metal complex, benzimidazolone, anthanthrone, anthraquinone, Quinacridone, dioxazine, perylene, thioindigo, triarylcarbonium or diketopyrrolopyrrole pigments; whose yellow preparation preferably contains a pigment from the group of the monoazo, disazo, benzimidazoline, isoindolinone, isoindoline or perinone pigments, in particular the Color Index Pigments Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow, Pigment Yellow Pigment Yellow 171, Pigment Yellow 176, Pigment Yellow 176, Pigment Yellow 176, Pigment Yellow 176, Pigment Yellow 171, Pigment Yellow 171, Pigment Yellow 171, Pigment Yellow 171, Pigment Yellow Pigment Yellow 191, Pigment Yellow 194, Pigment Yellow 196, Pigment Yellow 213 or Pigment Yellow 219; whose orange preparation preferably contains a pigment from the group of the disazo, β-naphthol, naphthol AS, benzimidazolone or perinone pigments, in particular the Color Index Pigments Pigment Orange 5, Pigment Orange 13, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 43, Pigment Orange 62, Pigment Orange 68, Pigment Orange 70, Pigment Orange 71, Pigment Orange 72, Pigment Orange 73, Pigment Orange 74 or Pigment Orange 81; whose green preparation preferably contains a pigment from the group of phthalocyanine pigments, in particular the Color Index pigments Pigment Green 7 or Pigment Green 36.

In addition, the ink sets and toner cartridges may also contain shading dyes, preferably from the group C.I. Acid Yellow 3, C.I. Food Yellow 3, C.I. Acid Yellow 17 and C.I. Acid Yellow 23; C.I. Direct Yellow 86, C.I. Direct Yellow 28, C.I. Direct Yellow 51, C.I. Direct Yellow 98 and C.I. Direct Yellow 132; C.I. Reactive Yellow 37; Direct Red 1, C.I. Direct Red 11, C.I. Direct Red 37, C.I. Direct Red 62, C.I. Direct Red 75, C.I. Direct Red 81, C.I. Direct Red 87, C.I. Direct Red 89, C.I. Direct Red 95, and C.I. Direct Red 227; CI Acid Red 1, CI Acid Red 8, CI Acid Red 18, CI Acid Red 52, CI Acid Red 80, CI Acid Red 81, CI Acid Red 82, CI Acid Red 87, CI Acid Red 94, CI Acid Red 115, CI Acid Red 131, CI Acid Red 144, CI Acid Red 152, CI Acid Red 154, CI Acid Red 186, CI Acid Red 245, CI Acid Red 249 and CI Acid Red 289; CI Reactive Red 21, CI Reactive Red 22, CI Reactive Red 23, CI Reactive Red 35, CI Reactive Red 63, CI Reactive Red 106, CI Reactive Red 107, CI Reactive Red 112, CI Reactive Red 113, CI Reactive Red 114, CI Reactive Red 126, CI Reactive Red 127, CI Reactive Red 128, CI Reactive Red 129, CI Reactive Red 130, CI Reactive Red 131, CI Reactive Red 137, CI Reactive Red 160, CI Reactive Red 161, CI Reactive Red 174 and CI Reactive Red 180, CI Acid Violet 48, CI Acid Violet 54, CI Acid Violet 66, CI Acid Violet 126, CI Acid Blue 1, CI Acid Blue 9, CI Acid Blue 80, CI Acid Blue 93, CI Acid Blue 93: 1, CI Acid Blue 182, CI Direct Blue 86, CI Direct Blue 199, CI Acid Green 1, CI Acid Green 16, CI Acid Green 25, CI Acid Green 81, CI Reactive Green 12, CI Acid Brown 126, CI Acid Brown 237, CI Acid Brown 289, CI Acid Black 194, CI Sulfur Black 1, CI Sulfur Black 2, C I. Sol. Sulfur Black 1, C.I. Reactive Black 5, C.I. Reactive Black 31, C.I. Reactive Black 8; wherein the reactive dyes may also be present in their partially or wholly hydrolyzed form.

Furthermore, the pigment compositions according to the invention are also suitable as colorants for color filters, both for additive and for subtractive color generation, and as colorants for electronic inks ("e-inks") or "electronic paper"("e-inks"). paper ").

In the production of color filters, both reflective and transparent color filters, pigments in the form of a paste or as pigmented photoresists in suitable binders (acrylates, acrylic esters, polyimides, polyvinyl alcohols, epoxies, polyesters, melamines, gelatin, caseins) on the respective LCD components (eg TFT-LCD = Thin Film Transistor Liquid Crystal Displays or eg (S) TN-LCD = (Super) Twisted Nematic LCD). In addition to a high thermal stability, a stable paste or a pigmented photoresist also requires high pigment purity (chroma). In addition, the pigmented color filters can also be applied by ink-jet printing or other suitable printing methods.

Synthetic Example 1:

a) Preparation of diazonium salt solution:

2200 g of e-water are introduced and 180 g of 3-amino-4-methoxybenzoic acid N-methylamide (1.0 mol) are interspersed and stirred in homogeneously at room temperature. After 15 minutes, cooled by addition of 800 g of ice and by additional external cooling to 2 ° C and then added 290 g of hydrochloric acid (31%). The precipitated hydrochloride is diazotized by addition of 179 g of sodium nitrite solution (40%) over 15 to 20 minutes at 5 to 10 ° C. The diazonium salt solution is stirred under an excess of nitrite for 1.5 h, then filtered off after addition of a clarifying agent and, if necessary, the nitrite excess is eliminated by adding sulfamic acid.

b) Preparation of a solution of the coupling component mixture:

There are introduced 2000 g of water and with stirring 186 g (0.67 mol) of N- (2-methylphenyl) -3-hydroxynaphthalene-2-carboxamide and 103 g (0.33 mol) of N- (3-nitrophenyl) -3 Hydroxynaphthalene-2-carboxamide registered, heated to 95 ° C and dissolved by adding 330 g of sodium hydroxide solution (33%) at 90 to 95 ° C within 2 minutes alkaline. It is then cooled to 80 to 60 ° C and held at this temperature. Possibly. the warm solution can be filtered while adding a clarifying agent.

c) azo coupling:

The clarified diazonium salt solution from a) is initially charged, adjusted by the addition of about 38 g of sodium acetate (in the form of a 4N solution) to pH 4.3 to 4.5 and cooled to 10 ° C. The coupler solution from b) is then metered in with stirring over the course of 1 to 1.5 h, the pH being kept at 4.8 to 5 by simultaneous addition of a total of about 190 g of hydrochloric acid (31% strength) , Then about 2.5 to 3 h or until the disappearance of the diazo component at RT to 30 ° C and pH 5 to 6 is stirred. After completion of the coupling reaction is heated for a further 1 h to about 50 ° C, then filtered and washed with water. After drying and grinding, 480 g of a bluish dark red pigment mixture containing the following pigments of the formulas (1) and (2) in a mass ratio of 65:35.

Synthetic Example 2:

• a) The preparation of the diazonium salt solution is carried out analogously to Synthesis Example 1a)
• b) The solution of the coupling component mixture is prepared analogously to Synthesis Example 1 b), except that 139 g (0.5 mol) of N- (2-methylphenyl) -3-hydroxynaphthalene-2-carboxamide and 154 g (0.5 mol) of N- (3-nitrophenyl) -3-hydroxynaphthalene-2-carboxylic acid amide.
• c) The azo coupling is carried out analogously to Synthesis Example 1c). After drying and grinding, 484 g of a bluish dark red pigment mixture containing the pigments of the formulas (1) and (2) in a mass ratio of 48.4: 51.6 are obtained.

Application examples:

A) Coloristic properties of pigment compositions in a toner system:

a) test toner:

(Reichhold polyester Fa Finetone ^® T 382 ES.) Is dispersed for preparing a test toner based on polyester, the pigment compositions at a concentration of 3 to 5% in a commercially available toner resin. For this purpose, the polyester is melted in a laboratory kneader and the pigment composition is added in portions. The dispersion time after entering the last pigment portion is 45 min.

b) Test system and measurement:

In order to obtain coloristic data in a toner medium which are as independent as possible from the type of machine used and are not dependent on the electrostatic loading, transfer rate, etc., the test toner prepared above is evaluated in a solvent varnish (30% finetone) to evaluate the coloristic properties of the pigment composition used ^® 382 ES in THF / ethyl acetate) and then applied with a handcoater rod No. 5, 50 μm wet film thickness on white test cards with / without black bars, 100 × 230 mm, 300 g / m ² . The application contains in each case 2.5% pigment composition.

The measurement of the color intensity and the color coordinates (Table 1) was carried out according to DIN 5033-7 ISO 7724-2 by means of a spectrophotometer (D65-10 ° observer, measuring geometry d / 8 ° under gloss inclusion). It measures the spectral reflectance and the colorimetry in the CIELAB system ( DIN 6170 . ISO7724-3 ) evaluated. The relative color intensity is determined by the weighted K / S sum ( DIN EN ISO 787-26 ).

The measurement of the optical density (CD) was carried out according to DIN 16536 by means of a densitometer from Gretag Macbeth under 45 ° / 0 ° ring optics DIN 5033 , Table 1: Test toner with L * a * b * Color strength in% C H OD 5% Synthesis Example 1 47.1 58.9 -10.3 130 59.74 348.66 1.65 3.5% Synthesis Example 1 51.0 56.8 -16.1 100 58.81 344.51 1:33 5% PR269 (comparison) 51.6 54.6 -13.5 96 56.29 346.49 1.25 5% PR184 (comparison) 52.0 55.9 -12.5 96 57.08 347.41 1.19

In this test system, the pigment composition according to the invention achieves a significantly higher color strength and a higher optical density (CD) than other naphthol azo pigments (for example PR 269, PR 184) which are customarily used in toners. At the same time, the chroma value C is higher.

c) Coloristic investigations using pain shakers (Table 2):

1 g of pigment or pigment composition with 50 g of 30% sodium Finetone varnish (30% Finetone ^® T 382 ES in ethyl acetate) and 25 g Mischoxidperlen (0.8 mm zirconium oxide beads stabilized Y) dispersed for 3 hours on a paint shaker. The colored solution with a laboratory printing machine (Labratester) (potentiometer 280, corresponding to 10 m / min)) (paper Algro Finess 80 g / ^m2) and transparency (Treofan GND ^® 50) applied. The sample and reference are applied next to each other. Three fields with different layer thicknesses are printed. The coloristic data are determined on the 3rd field (34 μm wet film thickness) (Table 2). TABLE 2 example pigment composition a * b * C h _from OD 1 Synthesis Example 1 (100%) 51.56 13.48 53.29 345.35 0.98 2 Synthesis Example 1 (90%) PR 122 (10%) 50.16 -13.94 52.06 344.46 0.93 3 Synthesis Example 1 (80%) PR 122 (20%) 49.67 -15.32 51.98 342.85 0.90 4 Synthesis Example 1 (70%) PR 122 (30%) 49.05 -15.3 51.38 342.68 0.88 5 Synthesis Example 1 (50%) PR 122 (50%) 47.29 -15.8 49.86 341.52 0.81 6 (compare) PR 269 (50%) PR 122 (50%) 43.61 -14.04 45.82 342.15 0.70 7 (compare) PR 269 (33%) PR 122 (66%) 42.94 -15.1 45.52 340.62 0.68 8 (compare) PR 269 46.34 -11.81 47.82 345.71 0.80 9 (compare) PR 122 41.48 -16.67 44.7 338.11 0.60

Examples 6 to 9 (comparative) are pigments and pigment mixtures commonly used in the toner field.

All pigment compositions according to the invention have higher chroma values C than the pigments or pigment mixtures commonly used. All pigment compositions according to the invention have higher optical density CD than the pigments or pigment mixtures commonly used.

d) Comparison with known magenta azo pigments:

Using the same test method as in Ab), pigment compositions according to the invention and various commercially available azo pigments were coloristically compared with the magenta pigment CI Pigment Red 184 (Table 3). Table 3: example pigment color strength dH dC dL there db transp. reference PR 184 100 0 0 0 0 0 ref 10 Synthetic Example 1 120 -2.4 1.14 -0.53 0.49 -2.61 4tra 11 Synthetic Example 2 133 -3.66 0.77 -0.91 -0.42 -3.72 5tra 12 (Cf.) PR 269 93 0.38 0.17 0.31 0.26 0.33 2tra 13 (Cf.) PR 185 96 10.47 0.55 1.4 2.23 10.24 4OP 14 (Cf.) PR 176 101 10.43 1.79 1.86 3.46 10 2OP 16 (Cf.) PR 146 84 8.38 -0.63 1.13 0.91 8.35 3op 18 (Cf.) PR 57: 1 91 3.4 -3.27 0.25 -2.34 4.09 2OP 19 (See) PR 147 93 0.46 -1.13 -0.08 -0.96 0.75 3op

Only the pigment compositions according to the invention have, compared with the reference, both high color strengths, a distinctly bluish hue and a positive chroma value, and, moreover, they show improved transparency in comparison to commercially available pigments (Comparative Examples 12-19).

e) Test in Chemical Toners:

In the preparation of suspension polymerization toners, polymerization is carried out in a two-phase system of water and monomer (styrene, acrylates) to produce the toner particles in the μm range. In order for the resulting particles to be colored in the desired hue, the pigment must be finely divided in the monomer phase and must not pass from the monomer phase into the aqueous phase during the process. Ie. the pigment must have an appropriate affinity for the monomer mixture used and must not be too hydrophilic as it would then enter the aqueous phase or be at the interface between monomer and water.

To test this property, proceed as follows:
2.5 g of pigment, 50 g of styrene are dispersed on a paintshaker with 150 g of glass beads for 60 min. After separating the beads, 9 g each of the pigment dispersion thus prepared in 3 different beakers are added to aqueous solutions with pH 11.4-6.9 and 1.5. Subsequently, the 3 solutions are stirred for 30 minutes by means of a magnetic stirrer. After stopping the stirrer, the phase separation and the location of the pigment (in the monomer phase or aqueous phase) are visually evaluated. Subsequently, the solutions are heated to 80 ° C and stirred again for 30 min. After stopping the stirrer, the phase separation and the location of the pigment are assessed visually.

Assessment: The quality of the phase separation is assessed visually for each of the 6 individual tests and "graded" with numbers between 1 and 3, where 1 is the best rating. Then, for each sample, the mean of the 6 individual scores is formed. The lower this value, the better the pigment for a suspension polymerization process, values less than 2 indicate that the pigment has suitable hydrophobicity (Table 4). TABLE 4 grading 1 2 3 observation Aqueous phase clear and not colored Aqueous phase slightly colored, but transparent Pigment in the aqueous phase;

The pigment compositions according to Synthesis Examples 1 and 2 according to the invention achieve a value (hydrophobicity index) of 1.7 in this test and are thus well suited for use in suspension polymerization processes.

Furthermore, when dispersing the pigments, it is important that the resulting dispersion in the monomer solution has a low viscosity value (<100 mPas). The pigment preparation according to the invention from synthesis examples 1 and 2 reaches z. B. a value of 36 mPas or 45 mPas, measured on a 5% dispersion of the pigment in styrene by means of a plate-cone rotary viscometer (6 mm / 2 ° cone) at 250 s ^-1 . This also shows that these pigment compositions are suitable for use in chemical toners such as suspension polymerization toners.

f) Electrostatic properties of the toner:

An important performance property of a toner is the electrostatic charging behavior. This is more or less influenced by the pigments used. To the influence of To assess pigment on the charging behavior of the toner, a test toner is prepared and then measured by means of a Q / M meter, the electrostatic chargeability of this test toner.

5 parts of the pigment composition according to the invention from Synthesis Example 1 are homogeneously incorporated as powder by means of a kneader into 95 parts of a toner binder (Styrene Acrylate: Almacryl B 1501) within 30 minutes.

It is then ground on a laboratory universal mill and then classified on a centrifugal separator. The desired particle fraction (4-25 microns) is activated with a carrier consisting of coated with styrene-methacrylate copolymer magnetite particles size of 50-200 mm (bulk density 2.62 g / cm ³ ) (FBM 100 A, Fa Powder Tech). The measurement is carried out on a standard Q / M measuring stand. By using a sieve with a mesh size of 25 microns ensures that the toner blows no carrier is entrained. The measurements are made at approx. 50% relative humidity and 22 ° C. Depending on the activation time, the following Q / M values are measured (Table 5): TABLE 5 pigment Charge control agent Triboelectric charge in μC / g after activation 5 min 10 min 30 min 2 h 24 hours 5% Synth.bsp 1 without -10 -11 -12 -14 -15 5% Synth.bsp 1 With 2% Bontron ^® E84 -23 -27 -30 -33 -32

The measurement results show that the pigment composition promotes the negative charging of the toner resin (charging without pigment about -5 μC / g) but does not dominate too much, so that by adding a small amount of a charge control agent, the toner charge can be adjusted according to requirements.

B) Application in ink-jet inks:

a) Coloristic properties in solvent inkjet inks:

For testing the color properties of the pigment compositions according to the invention was initially a pigment concentrate (3.5% pigment, 1.75% dispersing additive (Disperbyk ^® 2163), 9.5% VC / VAc copolymer, 85% LM mixture (cyclohexanone / butoxyethyl = For this purpose, the ingredients are dispersed for 120 min with 2 mm glass beads on a paint shaker.

1.6 g of the pigment concentrate thus prepared are diluted with 24 g of a 25% binder solution and mixed homogeneously. The pigment concentrate prepared in this way is applied to a soft PVC film (150 μm) using a handcoater No. 5 (50 μm wet film thickness).

When measuring with the colorimeter, the pigment composition of the invention is used as a reference (type) and the commercially available naphthol PR 147 and PR 184 measured against this type.

The commercially available naphthol pigments achieve color strengths similar to those of the pigment composition of the invention only at a concentration of approximately 3.5 times the amount. The hue of the comparative pigments is in each case distinctly yellower (dH = positive) and cloudier (dC = negative) than in the case of the pigment composition according to the invention (Table 6). Table 6: Pigment [%] Pigment conc. [%] Color strength [%] dH dC Synthetic Example 1 3.5 100 0 0 PR 147 (comparison) 12 * 105 2.12 -1.37 PR 184 (comparative) 12 * 107 6.36 -3.03 * The pigment concentration had to be increased to 12% in order to achieve comparable color strengths to Synthesis Example 1.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1195411A [0040]

Cited non-patent literature

• DIN 5033-7 [0067]
• ISO 7724-2 [0067]
• DIN 6170 [0067]
• ISO7724-3 [0067]
• DIN EN ISO 787-26 [0067]
• DIN 16536 [0068]
• DIN 5033 [0068]

Claims (15)

Use of pigment mixtures, each containing at least one pigment of the formulas (Ia) and (Ib),

in which X ¹ , X ^{3 are} independently of one another carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl or di (C ₁ -C ₄ ) - alkylsulfamoyl; X ² , X ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro; Y ¹ , Y ^{2 are} hydrogen, halogen or C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl; and Z ¹ , Z ^{2 are} hydrogen, phenyl, naphthyl, benzimidazolonyl, substituted phenyl or substituted naphthyl, where the substituents 1, 2, 3 or 4 in the number and selected from the group halogen, nitro, cyano, C ₁ -C ₄ - Alkoxycarbonyl, carbamoyl, C ₁ -C ₄ alkylcarbamoyl, di (C ₁ -C ₄ ) alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ alkylsulfamoyl, di (C ₁ -C ₄ ) alkylsulfamoyl, C ₁ -C ₄ acylamino, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and wherein the pigments of the formulas (Ia) and (Ib) are different. as a colorant in printing processes. Use according to claim 1, characterized in that the pigment mixture contains in each case at least one pigment of the formulas (IIa) and (IIb),

wherein independently of one another X ^{1 is} carbamoyl, C ₁ -C ₄ -alkylcarbamoyl, di (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ -alkylsulfamoyl or di (C ₁ -C ₄ ) -alkylsulfamoyl; X ^{2 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro; Y is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl; and Z ¹ , Z ^{2 are} hydrogen, phenyl, naphthyl, benzimidazolonyl, substituted phenyl or substituted naphthyl, where the substituents 1, 2, 3 or 4 in the number and selected from the group halogen, nitro, cyano, C ₁ -C ₄ - Alkoxycarbonyl, carbamoyl, C ₁ -C ₄ alkylcarbamoyl, di (C ₁ -C ₄ ) alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C ₁ -C ₄ alkylsulfamoyl, di (C ₁ -C ₄ ) alkylsulfamoyl, C ₁ -C ₄ acylamino, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and wherein the pigments of the formulas (IIa) and (IIb) are different. Use according to claim 1 or 2, characterized in that the pigment mixture in each case contains at least one pigment of the formulas (IIIa) and (IIIb),

in which, independently of one another, X ¹ denotes carbamoyl, C ₁ -C ₂ -alkylcarbamoyl or di (C ₁ -C ₂ ) -alkylcarbamoyl; Y is methyl, methoxy, ethyl or ethoxy; Z ^{1 is} phenyl or phenyl substituted by one, two or three radicals selected from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine; Z ^{2 have} the meaning nitrophenyl or cyanophenyl. Use according to claim 3, characterized in that X ^{1 is} carbamoyl or methylcarbamoyl; Y is methoxy; Z ^{1 is} methylphenyl and Z ^{2 is} nitrophenyl. Use according to one or more of claims 1 to 4, characterized in that the pigment mixtures 1 to 99 wt .-% of a component of formula (Ia), (IIa) or (IIIa) and 99 to 1 wt .-% of a component of Formula (Ib), (IIb) or (IIIb), each based on the total weight of the pigment mixture. Use according to one or more of claims 1 to 5, characterized in that adjuvants from the group of surfactants, pigmentary or non-pigmentary dispersants, fillers, extenders, resins, waxes, defoamers, antidusting agents, extenders, colorants for shading, preservatives, drying retardants , Additives for controlling the rheology, wetting agents, antioxidants, UV absorbers, light stabilizers, or a combination thereof are included. Use according to claim 6, characterized in that the colorant for nuancing is a quinacridone pigment or a naphthol AS pigment, which is different from the compound of formula (Ia) and (Ib). Use according to one or more of claims 1 to 7, characterized in that the printing method is an offset printing, flexographic or gravure printing method. Use according to one or more of claims 1 to 8, characterized in that the printing process is a non-impact printing process. Use according to claim 9, characterized in that the non-impact printing process comprises electrophotography, ink-jet printing, use in electronic inks and the production of color filters. Printing ink containing a pigment mixture according to one or more of claims 1 to 8. An electrophotographic toner or developer containing a pigment mixture according to one or more of claims 1 to 7. Inkjet ink containing a pigment mixture according to one or more of claims 1 to 7. Toner cartridge set containing a yellow, magenta, cyan and black toner cartridge, wherein the magenta cartridge contains a pigment mixture according to one or more of claims 1 to 7. An inkjet ink set containing a yellow, magenta, cyan and black ink cartridge, wherein the magenta ink cartridge contains a pigment mixture according to one or more of claims 1 to 7.